In Situ Spectroscopic Characterization and Theoretical Calculations Identify Partially Reduced ZnO_1-x /Cu Interfaces for Methanol Synthesis from CO₂

The active site of the industrial Cu/ZnO/Al₂ O₃ catalyst used in CO₂ hydrogenation to methanol has been debated for decades. Grand challenges remain in the characterization of structure, composition, and chemical state, both microscopically and spectroscopically, and complete theoretical calculations are limited when it comes to describing the intrinsic activity of the catalyst over the diverse range of structures that emerge under realistic conditions. Here a series of inverse model catalysts of ZnO on copper hydroxide were prepared where the size of ZnO was precisely tuned from atomically dispersed species to nanoparticles using atomic layer deposition. ZnO decoration boosted methanol formation to a rate of 877 g_MeOH  kg_cat ^-1  h^-1 with ≈80 % selectivity at 493 K. High pressure in situ X-ray absorption spectroscopy demonstrated that the atomically dispersed ZnO species are prone to aggregate at oxygen-deficient ZnO ensembles instead of forming CuZn metal alloys. By modeling various potential active structures, density functional theory calculations and microkinetic simulations revealed that ZnO/Cu interfaces with oxygen vacancies, rather than stoichiometric interfaces, Cu and CuZn alloys were essential to catalytic activation.